A new convenient route for the synthesis of poly(ɛ-caprolactone) (PCL) with α,ω-telechelic diols' end-groups is presented. Synthesis of α,ω-telechelic PCL diols (HOPCLOH) was achieved by ring-opening polymerization (ROP) of ɛ-caprolactone (CL) catalyzed with ammonium decamolybdate (NH 4) 8[Mo 10O 34] and using diethylene glycol (DEG) as initiator. Obtained HOPCLOH was characterized by 1H and 13C NMR, FT-IR, GPC and MALDI-TOF. Comparative studies demonstrate that ammonium decamolybdate (NH 4) 8[Mo 10O 34] is better catalyst than Sn-octanoate (SnOct 2) toward CL polymerization in presence of DEG, under the conditions tested. A biodegradable poly(ester-urethane-urea) derivative was efficiently prepared from synthesized HOPCLOH. Obtained polymer shows minor differences with respect to the properties recorded for a poly(ester-urethane-urea) obtained from commercial HOPCLOH.